O2 Exposure Research Articles

Interplay of Surface Hydride, Hydrogen Evolution, and Oxygen Reduction on Cu(111)

Copper is presently the material of choice for hydrogenation reactions converting CO2 or CO to hydrocarbons and oxygenates although the identity and role of adsorbed reaction intermediates remains unresolved and understudied. Accordingly, the interactions between C, O, H, and molecules comprised thereof, with different Cu surfaces, defects and applied potentials are of substantial interest. This talk will focus on the dynamic interplay between surface hydride formation, hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR) on Cu(111) in perchloric acid electrolyte using electrochemical mass spectrometry (EC-MS). Voltammetric EC-MS unveils a two-stage process for surface hydride formation, with recombination to H2 occurring at specific potentials. Controlled introduction of O2 into the cell does not disrupt hydride coverage, while its recombination potential correlates with the transition from mass-transport-limited ORR kinetics to mixed control ORR kinetics. Concurrent ORR accelerates steady-state HER onset, with a sharp increase in transient H2 production upon potential stepping. Furthermore, convolved voltammetric waves suggest surface restructuring due to O2 exposure post-ORR. These findings elucidate the complex interactions between surface species and electrochemical behavior, shedding light on Cu's catalytic selectivity and the impact of O2 on its electrochemical properties.

The surface chemistry of the atomic layer deposition of ruthenium on aluminum and tantalum oxide surfaces

The surface chemistry of Ru atomic layer deposition (ALD) processes based on the use of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) (Ru(tmhd)3) and either molecular oxygen or atomic hydrogen on aluminum oxide films was characterized by a combination of surface-sensitive techniques. The thermal decomposition of the Ru metalorganic precursor was determined, by using a combination of reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS), to start below 400 K and to take place in a stepwise fashion over a wide range of temperatures. Gas-phase products from this chemistry include 2,2,6,6-tetramethyl-3,5-heptanedione (the protonated ligand, Htmhd; in a TPD peak at 520 K), isobutene (540 K; indicating the fragmentation of the organic ligands), and other products from isomerization and/or aldol condensation (650 and 730 K). This chemistry is accompanied by the reduction of the Ru3+ ions in two stages, involving the loss of some of their ligands and their direct bonding to the substrate first (between 500 and 600 K) and a full reduction to a metallic state later on (600–700 K). ALD cycles using either molecular oxygen or atomic hydrogen resulted in the slow build-up of Ru on the surface, but the co-deposition of carbon could not be avoided, at least in the initial cycles, while the alumina surface was still exposed. With O2, the Ru atoms alternate between partially-oxidized (after the O2 exposures) and zero-valent (after the Ru(tmhd)3 doses) states, and some Ru loss in the form of the volatile RuO4 oxide was seen after the second half of the ALD cycles; neither the Ru oxidation state alternation nor the elimination of some Ru from the surface were observed when using H·. The deposited Ru was determined, by combining results from angle-resolved XPS (ARXPS) and low-energy ion scattering (LEIS) experiments, to grow as 3D nanoparticles rather than as a layer-by-layer 2D film, presumably because the Ru precursor preferentially adsorbs (and decomposes more cleanly) on the metal surface. A discussion is provided of the implications of these results for the design of ALD processes.

Metaproteomics-informed stoichiometric modeling reveals the responses of wetland microbial communities to oxygen and sulfate exposure

Climate changes significantly impact greenhouse gas emissions from wetland soil. Specifically, wetland soil may be exposed to oxygen (O2) during droughts, or to sulfate (SO42-) as a result of sea level rise. How these stressors – separately and together – impact microbial food webs driving carbon cycling in the wetlands is still not understood. To investigate this, we integrated geochemical analysis, proteogenomics, and stoichiometric modeling to characterize the impact of elevated SO42- and O2 levels on microbial methane (CH4) and carbon dioxide (CO2) emissions. The results uncovered the adaptive responses of this community to changes in SO42- and O2 availability and identified altered microbial guilds and metabolic processes driving CH4 and CO2 emissions. Elevated SO42- reduced CH4 emissions, with hydrogenotrophic methanogenesis more suppressed than acetoclastic. Elevated O2 shifted the greenhouse gas emissions from CH4 to CO2. The metabolic effects of combined SO42- and O2 exposures on CH4 and CO2 emissions were similar to those of O2 exposure alone. The reduction in CH4 emission by increased SO42- and O2 was much greater than the concomitant increase in CO2 emission. Thus, greater SO42- and O2 exposure in wetlands is expected to reduce the aggregate warming effect of CH4 and CO2. Metaproteomics and stoichiometric modeling revealed a unique subnetwork involving carbon metabolism that converts lactate and SO42- to produce acetate, H2S, and CO2 when SO42- is elevated under oxic conditions. This study provides greater quantitative resolution of key metabolic processes necessary for the prediction of CH4 and CO2 emissions from wetlands under future climate scenarios.

Normobaric Hyperoxia Treatment after Mid-cervical Contusion Injury in Rats

Severe hypoxia at or near the site of spinal cord injury (SCI) contributes to necrosis and secondary tissue damage. Prior studies of O2 therapy after SCI have primarily used pressurized hyperoxic exposure ( i.e., hyperbaric oxygen). We tested the hypothesis that daily exposure to 100% O2, delivered at atmospheric pressure ( i.e., normobaric hyperoxia) could accelerate the recovery of inspiratory tidal volume after cervical SCI. Three groups of adult male Sprague Dawley rats received a 150 kdyn impact right lateral C4 cervical SCI. In group 1, normobaric hyperoxia (100% O2 at 1 atmosphere pressure, 2 hours) was initiated within 20 min of SCI and continued daily for 7 days. In group 2, the same normobaric hyperoxia paradigm was initiated on day 8 post-injury and continued until day 14. A third group received a sham treatment, consisting of exposure to normobaric normoxia (21% O2, 1 ATA) daily for 14 days. Whole-body plethysmography was used to examine breathing patterns before-, 1-, and 2-weeks post-SCI. All three groups lost and then gained body mass at similar rates over days 1-14 post-SCI. Mortality rates during the first week after SCI were 23% (5/22) in rats not exposed to hyperoxia, and 10% (1/10) in the daily hyperoxia group. Tidal volume (VT) and breathing rate were compared using 2-way repeated measures ANOVA. The breathing rate (br/min) was similar between groups at 1-week post-injury. We observed a trend (p=0.182) for reduced breathing rate at the 2-week time point in the week-1 hyperoxia group (69±18) compared to the week-2 hyperoxia group (89±21) and the normoxia group (83±17). Inspiratory VT (mL/breath) was elevated in the week-1 hyperoxia group (0.59±0.08) as compared to the week-2 hyperoxia (0.44±0.05) and normoxia groups (0.44±0.06) at 1-week post-SCI (p=0.002). When VT was normalized to body weight (mL/breath/kg) the same effect of O2 exposure was observed (p=0.001). The effect was transient, however, and at day 14 post-SCI VT was similar across the three experimental groups (p>0.50). We conclude that normobaric hyperoxia treatment during the first week after cervical SCI alters the pattern of breathing, and may have benefit to recovery. R01HL153140-04. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

Markers of sensory dynamics in phenols-rich virgin olive oils under optimal storage conditions

Early changes in sensory quality of phenols-rich virgin olive oil (VOO) and their relationship with the chemical changes are less studied in the literature. Therefore, the objective of this study was to propose a predictive model of dynamics of sensory changes based on specific chemical markers. The evolution of the sensory quality of phenol-rich VOOs from Tuscan cultivars stored under optimal storage conditions (i.e., absence of light, no O2 exposure, low temperature) was investigated using a multi-step methodological approach combining sensory (official sensory analysis (so-called Panel Test), Descriptive Analysis and Temporal Dominance of Sensation) and chemical measurements. The sensory map from descriptive data was related to the phenolic and volatile profiles, measured using HPLC-DAD and HS-SPME-GC–MS, respectively. A predictive model of the sensory changes over storage based on chemical compounds was developed. Results showed that very early changes involving phenolic and volatile compounds profiles occur in VOOs stored under optimal storage conditions, which turn in changes in sensory properties evaluated by the official panel test, the descriptive analysis and the temporal dominance of sensation. Furthermore, a chemical marker of sensory dynamics of oils during storage was identified as the ratio between two groups of secoiridoids. The proposed model, supported by the mentioned chemical marker, has the potential of improving the control of sensory changes in phenols-rich virgin olive oils during storage in optimal conditions.

Short-term hyperoxia-induced functional and morphological changes in rat hippocampus.

Excess oxygen (O2) levels may have a stimulating effect, but in the long term, and at high concentrations of O2, it is harmful to the nervous system. The hippocampus is very sensitive to pathophysiological changes and altered O2 concentrations can interfere with hippocampus-dependent learning and memory functions. In this study, we investigated the hyperoxia-induced changes in the rat hippocampus to evaluate the short-term effect of mild and severe hyperoxia. Wistar male rats were randomly divided into control (21% O2), mild hyperoxia (30% O2), and severe hyperoxia groups (100% O2). The O2 exposure lasted for 60 min. Multi-channel silicon probes were used to study network oscillations and firing properties of hippocampal putative inhibitory and excitatory neurons. Neural damage was assessed using the Gallyas silver impregnation method. Mild hyperoxia (30% O2) led to the formation of moderate numbers of silver-impregnated "dark" neurons in the hippocampus. On the other hand, exposure to 100% O2 was associated with a significant increase in the number of "dark" neurons located mostly in the hilus. The peak frequency of the delta oscillation decreased significantly in both mild and severe hyperoxia in urethane anesthetized rats. Compared to normoxia, the firing activity of pyramidal neurons under hyperoxia increased while it was more heterogeneous in putative interneurons in the cornu ammonis area 1 (CA1) and area 3 (CA3). These results indicate that short-term hyperoxia can change the firing properties of hippocampal neurons and network oscillations and damage neurons. Therefore, the use of elevated O2 concentration inhalation in hospitals (i.e., COVID treatment and surgery) and in various non-medical scenarios (i.e., airplane emergency O2 masks, fire-fighters, and high altitude trekkers) must be used with extreme caution.

Profiles of oxygen and titanium point defects in ferromagnetic TiO2 films

Experimentally it is shown that without any oxygen manipulation for TiO2, a strong room temperature ferromagnetism could be expected only in ultra-thin films, with the ideal thickness below 100 nm. Both bulks and nano-powders of TiO2 are diamagnetic, indicating that the surface and its nano-sublayers play very important roles in tailoring the magnetic properties in this type of compound. To shed a new light on the defect-related magnetism in the typical case of anatase TiO2 surfaces, we have performed a series of quantum-mechanical calculations for TiO2 slabs containing Ti or O vacancies in different distances from the (001) surface. The lowest formation energies were obtained for the Ti vacancies in the first sub-surface layer and the O vacancies within the surface. The computed magnetic states reflect complicated structural relaxations of atoms influenced by both the surface and vacant atomic positions. O atoms cannot contribute much to magnetic moment when Ti vacancies are isolated and far from the surface. Ti vacancies in TiO2 are only metastable. The formation energy of Ti interstitials is lower than for Ti vacancies since high-temperature annealing, especially with a lot of O2 available that would fill up O-related defects, and as a result, eliminate most of Ti vacancies. Lower temperatures, less O2, and shorter exposure times may enable not only partial elimination of Ti vacancies but also can facilitate their diffusion into different states of aggregations. In the ferromagnetic films (i.e. thin films below 100 nm), it looks like that the O atoms are located closer to the Ti vacancies.

Probing Catalytic Sites and Adsorbate Spillover on Ultrathin FeO2-x Film on Ir(111) during CO Oxidation.

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising potential for low-temperature CO catalytic oxidation, but the temporal and spatial distribution of active sites during the reaction and how molecular-scale structures develop at the interface are not fully understood. Here, we studied the catalytic CO oxidation and the effect of co-adsorbed hydrogen on the FeO2-x/Ir(111) surface. Combining scanning tunneling microscopy (STM), isotope-labeled pulse reaction measurements, and DFT calculations, we identified both FeO2/Ir and FeO2/FeO sites as active sites with different reactivity. The trilayer O-Fe-O structure with its Moiré pattern can be fully recovered after O2 exposure, where molecular O2 dissociates at the FeO/Ir interface. Additionally, as a competitor, dissociated hydrogen migrates onto the oxide film with the formation of surface hydroxyl and water clusters down to 150 K.

Cyanuric Acid-Functionalized Perovskite Nanocrystals toward Low Interface Impedance, High Environmental Stability, and Superior Electrochemiluminescence.

Perovskite nanocrystals (PNs) have received much attention as luminescence materials in the field of electrochemiluminescence (ECL). However, as one key factor for determining the optoelectronic properties of the surface state of PNs, the surface passivation layer of PNs has enormous difficulty in simultaneously meeting the requirements of high ECL efficiency, conductivity, and stability. Herein, an effective surface modification strategy with cyanuric acid (CA) is used to solve such issue. As confirmed, the CA molecules are chemically anchored onto the surface of PNs via the Lewis interaction between π electrons of the triazine ring and the empty orbit of Pb2+. Benefiting from the above interaction, the electrochemical impedance of PNs is decreased greatly without the loss of light-emitting efficiency. Moreover, the stability of PNs under O2 exposure is improved by almost sixfold. These improvements are confirmed to be beneficial for enhancing the ECL behaviors of PNs under electrochemical operation. Upon cathode ECL driving conditions in aqueous media, the ECL intensity and efficiency of PNs are increased to 200 and 170%, respectively. This work provides a new modification strategy to holistically improve the ECL performance of PNs, which is instructive to exploring robust perovskite nanomaterials for electrochemical applications.

Synthesis, Structure and Reactivity of a Mononuclear N,N,O-Bound Fe(II) α-Keto-Acid Complex.

A bulky, tridentate phenolate ligand (ImPh2 NNOtBu ) was used to synthesise the first example of a mononuclear, facial, N,N,O-bound iron(II) benzoylformate complex, [Fe(ImPh2 NNOtBu )(BF)] (2). The X-ray crystal structure of 2 reveals that the iron centre is pentacoordinate (τ=0.5), with a vacant site located cis to the bidentate BF ligand. The Mössbauer parameters of 2 are consistent with high-spin iron(II), and are very close to those reported for α-ketoglutarate-bound non-heme iron enzyme active sites. According to NMR and UV-vis spectroscopies, the structural integrity of 2 is retained in both coordinating and non-coordinating solvents. Cyclic voltammetry studies show that the iron centre has a very low oxidation potential and is more prone to electrochemical oxidation than the redox-active phenolate ligand. Complex 2 reacts with NO to form a S=3 /2 {FeNO}7 adduct in which NO binds directly to the iron centre, according to EPR, UV-vis, IR spectroscopies and DFT analysis. Upon O2 exposure, 2 undergoes oxidative decarboxylation to form a diiron(III) benzoate complex, [Fe2 (ImPh2 NNOtBu )2 (μ2 -OBz)(μ2 -OH)2 ]+ (3). A small amount of hydroxylated ligand was also observed by ESI-MS, hinting at the formation of a high-valent iron(IV)-oxo intermediate. Initial reactivity studies show that 2 is capable of oxygen atom transfer reactivity with O2 , converting methyl(p-tolyl)sulfide to sulfoxide.

Larger hydroxyapatite aggregation from Ca2+ adhesion in ANAMMOX granular sludge caused by high dissolved oxygen

Anaerobic ammonia oxidation (ANAMMOX), a sustainable biological process, is promising to remove NH4+-N from municipal sewage. In this study, results showed that the anammox granular sludge morphology changes with the alternation of dissolved oxygen (DO), mainly attributing to the adhesion of calcium ions (Ca2+) to the surface of sludge particles. Diverse characterization methods revealed that gray adhesions in the form of hydroxyapatite covered the original holes on the anammox granular sludge surface, including scanning Electron Microscopy (SEM), digital camera images, Energy Dispersive Spectrometer (EDS), and X-ray diffraction (XRD). Ex-situ degradation of NH4+-N and NO2−-N yielded diverse outcomes. The protein to polysaccharide ratio (PN/PS) in the total extracellular polymeric substances (EPS) across 4 size groups demonstrated a decrease under O2 exposure. Microbial community analysis indicated norank_f_A4b and Nitrolancea being the most abundant genus under O2 exposure at day 1 and day 100, respectively. These findings offer an effective strategy to prevent size-larger granular sludge from deteriorating through changing DO and Ca2+ in municipal wastewater in ANAMMOX.

Activity and adsorption behavior of oxygen on rutile TiO2(110)

The activity and adsorption behavior of oxygen on rutile TiO2(110) (RTiO2(110)) were investigated using the temperature programmed desorption (TPD) method with methanol (CH3OH) as the probe molecule. By controlling the coverage of molecular O2 on the surface via increasing or decreasing O2 exposure, two chemisorbed O2 species on the surface are confirmed, one at the bridging oxygen vacancy (OV) site (O22-/Ov) and the other at the five-fold coordinated titanium (Ti5c) site (O22--/Ti5c). At low O2 exposure, O22--/OV is the main species on the surface, which only leads to the O–H bond cleavage of CH3OH, producing methoxy groups (CH3O). However, after the OV sites are nearly filled by O2 at about 0.1 L O2 exposure, O2/Ti5c species begins to appear on R-TiO2(110) surface, resulting in the formation of formaldehyde (CH2O) via the reaction of O2/Ti5c species with CH3OH or CH3O to break the C-H bond at low surface temperature. Moreover, the yield of CH2O increases linearly with that of H2O. In addition, when the 1 L O2 covered surface is irradiated with 355 nm UV irradiation to desorb and dissociate O2/Ti5c species, the yield of CH2O decreases linearly with that of H2O. Further analysis suggests that the charge state of O2/Ti5c may not change as the exposure of O2 changes on the R-TiO2(110) surface, and O2 is most likely to adsorb on the Ti5c sites in the form of O22-, not O2−. The result not only advances our understanding on the adsorption state of O2 on TiO2, but also provides clues for low temperature C–H bond activation with O2 on TiO2.

Degradation of GaN field emitter arrays induced by O2 exposure

Field emitter arrays (FEAs) have the potential to operate at high frequencies and in harsh environments. However, they have been shown to degrade under oxidizing environments. Studying the effect of O2 on FEAs can help to understand the degradation mechanisms, identify the requirements for vacuum packaging, and estimate the lifetime of the device. In this work, the effect of O2 exposure on 100 × 100 gallium-nitride-field emitter arrays (GaN-FEAs) was studied. The GaN-FEAs were operated at 6 × 10−10 Torr with a 1000 V DC anode voltage and a 50 V DC gate voltage, where the anode current was 1 μA and the gate current was ≤4 nA. The devices were exposed to 10−7, 10−6, and 10−5 Torr of O2 for 100 000 L. The anode current dropped by 50% after 300 L and 98% after 100 000 L. It was observed that the degradation depends on the exposure dose, rather than pressure. The devices mostly degrade when they are ON, confirmed by exposing the device to O2 when the gate voltage was off, and also by the relation between the degradation and duty cycle when pulsing the gate. The results of O2 exposure were compared to Ar exposure to determine whether sputtering and changes in the surface geometry were the primary cause of degradation. The results suggest that changes in the work function and surface chemistry are the cause of emission degradation of GaN-FEA induced by O2.

What could be the low-temperature limit of atomic layer deposition of platinum using MeCpPtMe3 and oxygen?

We explore the low-temperature limit of atomic layer deposition of Pt using MeCpPtMe3 and O2. We reveal that by supplying a sufficiently high O2 exposure, highly dispersed and thermally stable Pt sub-nanometer clusters can be deposited onto the surface of P25 TiO2 nanoparticles even at room temperature by atmospheric-pressure ALD.

Substrate-dependent oxidative inactivation of a W-dependent formate dehydrogenase involving selenocysteine displacement.

Metal-dependent formate dehydrogenases are very promising targets for enzyme optimization and design of bio-inspired catalysts for CO2 reduction, towards innovative strategies for climate change mitigation. For effective application of these enzymes, the catalytic mechanism must be better understood, and the molecular determinants clarified. Despite numerous studies, several doubts persist, namely regarding the role played by the possible dissociation of the SeCys ligand from the Mo/W active site. Additionally, the oxygen sensitivity of these enzymes must also be understood as it poses an important obstacle for biotechnological applications. This work presents a combined biochemical, spectroscopic, and structural characterization of Desulfovibrio vulgaris FdhAB (DvFdhAB) when exposed to oxygen in the presence of a substrate (formate or CO2). This study reveals that O2 inactivation is promoted by the presence of either substrate and involves forming a different species in the active site, captured in the crystal structures, where the SeCys ligand is displaced from tungsten coordination and replaced by a dioxygen or peroxide molecule. This form was reproducibly obtained and supports the conclusion that, although W-DvFdhAB can catalyse the oxidation of formate in the presence of oxygen for some minutes, it gets irreversibly inactivated after prolonged O2 exposure in the presence of either substrate.

An allosteric redox switch involved in oxygen protection in a CO2 reductase.

Metal-dependent formate dehydrogenases reduce CO2 with high efficiency and selectivity, but are usually very oxygen sensitive. An exception is Desulfovibrio vulgaris W/Sec-FdhAB, which can be handled aerobically, but the basis for this oxygen tolerance was unknown. Here we show that FdhAB activity is controlled by a redox switch based on an allosteric disulfide bond. When this bond is closed, the enzyme is in an oxygen-tolerant resting state presenting almost no catalytic activity and very low formate affinity. Opening this bond triggers large conformational changes that propagate to the active site, resulting in high activity and high formate affinity, but also higher oxygen sensitivity. We present the structure of activated FdhAB and show that activity loss is associated with partial loss of the metal sulfido ligand. The redox switch mechanism is reversible in vivo and prevents enzyme reduction by physiological formate levels, conferring a fitness advantage during O2 exposure.

GSDMD gene knockout alleviates hyperoxia-induced hippocampal brain injury in neonatal mice

BackgroundNeonatal hyperoxia exposure is associated with brain injury and poor neurodevelopment outcomes in preterm infants. Our previous studies in neonatal rodent models have shown that hyperoxia stimulates the brain’s inflammasome pathway, leading to the activation of gasdermin D (GSDMD), a key executor of pyroptotic inflammatory cell death. Moreover, we found pharmacological inhibition of caspase-1, which blocks GSDMD activation, attenuates hyperoxia-induced brain injury in neonatal mice. We hypothesized that GSDMD plays a pathogenic role in hyperoxia-induced neonatal brain injury and that GSDMD gene knockout (KO) will alleviate hyperoxia-induced brain injury.MethodsNewborn GSDMD knockout mice and their wildtype (WT) littermates were randomized within 24 h after birth to be exposed to room air or hyperoxia (85% O2) from postnatal days 1 to 14. Hippocampal brain inflammatory injury was assessed in brain sections by immunohistology for allograft inflammatory factor 1 (AIF1) and CD68, markers of microglial activation. Cell proliferation was evaluated by Ki-67 staining, and cell death was determined by TUNEL assay. RNA sequencing of the hippocampus was performed to identify the transcriptional effects of hyperoxia and GSDMD-KO, and qRT-PCR was performed to confirm some of the significantly regulated genes.ResultsHyperoxia-exposed WT mice had increased microglia consistent with activation, which was associated with decreased cell proliferation and increased cell death in the hippocampal area. Conversely, hyperoxia-exposed GSDMD-KO mice exhibited considerable resistance to hyperoxia as O2 exposure did not increase AIF1 + , CD68 + , or TUNEL + cell numbers or decrease cell proliferation. Hyperoxia exposure differentially regulated 258 genes in WT and only 16 in GSDMD-KO mice compared to room air-exposed WT and GSDMD-KO, respectively. Gene set enrichment analysis showed that in the WT brain, hyperoxia differentially regulated genes associated with neuronal and vascular development and differentiation, axonogenesis, glial cell differentiation, hypoxia-induced factor 1 pathway, and neuronal growth factor pathways. These changes were prevented by GSDMD-KO.ConclusionsGSDMD-KO alleviates hyperoxia-induced inflammatory injury, cell survival and death, and alterations of transcriptional gene expression of pathways involved in neuronal growth, development, and differentiation in the hippocampus of neonatal mice. This suggests that GSDMD plays a pathogenic role in preterm brain injury, and targeting GSDMD may be beneficial in preventing and treating brain injury and poor neurodevelopmental outcomes in preterm infants.

Aperiodic Modulation of Graphene Driven by Oxygen-Induced Reconstruction of Rh(110).

Artificial nanostructuring of graphene has served as a platform to induce variations in its structural and electronic properties, fostering the experimental observation of a wide and fascinating phenomenology. Here, we present an approach to graphene tuning, based on Rh(110) surface reconstruction induced by oxygen atoms intercalation. The resulting nanostructured graphene has been characterized by scanning tunneling microscopy (STM) complemented by low-energy electron microscopy (LEEM), micro low-energy electron diffraction (μ-LEED), micro angle-resolved photoemission spectroscopy (μ-ARPES), and micro X-ray photoelectron spectroscopy (μ-XPS) measurements under ultrahigh vacuum (UHV) conditions at room temperature (RT). It is found that by fine-tuning the O2 exposure amount, a mixture of missing row surface reconstructions of the metal surface below the graphene layer can be induced. This atomic rearrangement under the graphene layer results in aperiodic patterning of the two-dimensional (2D) material. The electronic structure of the resulting nanostructured graphene is dominated by a linear dispersion of the Dirac quasiparticles, characteristic of its free-standing state but with a p-doping character. The local effects of the underlying missing rows on the interfacial chemistry and on the quasiparticle scattering processes in graphene are studied using atomically resolved STM images. The possibilities offered by this nanostructuring approach, which consists in inducing surface reconstructions under graphene, could provide a novel tuning strategy for this 2D material.

Oxygen and moisture-induced healing of halide double perovskite surface defects.

In this work, we studied the impact of environmental constituents such as oxygen (O2) and moisture on halide double perovskite (HDP) films. The transport measurements indicate that an increment in O2 concentration enhances the resistivity of a Cs2AgBiBr6 film by two orders of magnitude. The adsorption of O2 on the film's surface helps in passivation of defects (∼50% reduction in defect density on O2 exposure), which inhibits ion migration and results in an increased resistivity of the film. The process of adsorption and desorption of O2 on the film surface is found to be fully reversible. In contrast, the resistivity of double perovskite films decreases by an order of magnitude in the presence of moisture. This is attributed to the generation of free protons as a result of the dissociation of water molecules at the films' surface, hence exhibiting an increase in current under external bias. The HDP films possess high resistivity (for T < 100°C) due to the desorption of physisorbed water layers from the surface, which gradually decreases with an increase in the operating temperature. This work demonstrates that O2 and moisture are a good combination for defect passivation in any HDPs, in general.

Brief Oxygen Exposure after Traumatic Brain Injury Hastens Recovery and Promotes Adaptive Chronic Endoplasmic Reticulum Stress Responses.

Traumatic brain injury (TBI) is a major public health concern, particularly in adolescents who have a higher mortality and incidence of visual pathway injury compared to adult patients. Likewise, we have found disparities between adult and adolescent TBI outcomes in rodents. Most interestingly, adolescents suffer a prolonged apneic period immediately post-injury, leading to higher mortality; therefore, we implemented a brief oxygen exposure paradigm to circumvent this increased mortality. Adolescent male mice experienced a closed-head weight-drop TBI and were then exposed to 100% O2 until normal breathing returned or recovered in room air. We followed mice for 7 and 30 days and assessed their optokinetic response; retinal ganglion cell loss; axonal degeneration; glial reactivity; and retinal ER stress protein levels. O2 reduced adolescent mortality by 40%, improved post-injury visual acuity, and reduced axonal degeneration and gliosis in optical projection regions. ER stress protein expression was altered in injured mice, and mice given O2 utilized different ER stress pathways in a time-dependent manner. Finally, O2 exposure may be mediating these ER stress responses through regulation of the redox-sensitive ER folding protein ERO1α, which has been linked to a reduction in the toxic effects of free radicals in other animal models of ER stress.